Azeotrope-like compositions comprising 1-chloro-3,3,3-trifluoropropene

ABSTRACT

An azeotrope-like mixture consisting essentially of a binary azeotrope-like mixture consisting essentially of trans-1-chloro-3,3,3-trifluoropropene (trans-HFO-1233zd) and a second component selected from the group consisting of 2,3,3,3-tetrafluoropropene (HFO-1234yf) and trans-1,3,3,3-tetrafluoropropene (trans-HFO-1234ze), and combinations of these and various uses thereof.

CROSS REFERENCES TO RELATED APPLICATIONS

This application is a divisional filing of U.S. application Ser. No.13/296,664, filed Nov. 15, 2011, now U.S. Pat. No. 8,734,671, which isrelated to and claims the priority benefit of U.S. provisionalapplication No. 61/415,670 filed Nov. 19, 2010, the contents each ofwhich are incorporated herein by reference.

FIELD OF THE INVENTION

The present invention relates generally to compositions comprising1-chloro-3,3,3-trifluoropropene. More specifically, the presentinvention provides azeotrope-like compositions comprising1-chloro-3,3,3-trifluoropropene and uses thereof.

BACKGROUND OF THE INVENTION

Fluorocarbon based fluids, including chlorofluorocarbons (“CFCs”),hydrochlorofluorocarbons (“HCFCs”), and hydrofluorolefins (“HFOs”), haveproperties that are desirable in industrial refrigerants, blowingagents, heat transfer media, solvents, gaseous dielectrics, and otherapplications. For these applications, the use of single component fluidsor azeotrope-like mixtures, i.e., those which do not substantiallyfractionate on boiling and evaporation, are particularly desirable. Itis also considered important in many applications, including withrespect to heat transfer fluids, blowing agents, propellants, solventsand aerosols, that any potential substitute also preferably possessthose properties present in many of the most widely used fluids, such asexcellent functional properties (for example, heat transfer propertiesin the case of heat transfer compositions), chemical stability, low- orno-toxicity, low- or no-flammability and/or lubricant compatibility,among others.

Unfortunately, suspected environmental problems, such as global warmingand ozone depletion, and other potential problems such as a flammabilitylevel that is higher than desired, have been attributed to the use ofsome of these fluids, thereby limiting their contemporary use.Hydrofluoroolefins (“HFOs”) have been proposed as possible replacementsfor such CFCs, HCFCs, and HFCs. However, the identification of new,environmentally-safe, non-fractionating mixtures comprising HFOs arecomplicated due to the fact that azeotrope formation is not readilypredictable. Therefore, industry is continually seeking new HFO-basedmixtures that are acceptable and environmentally safer substitutes forCFCs, HCFCs, HFCs and certain HFOs and mixtures of these.

This invention satisfies one or more of the above-noted or other needs.

SUMMARY OF INVENTION

Applicants have discovered azeotrope and azeotrope-like compositionscomprising, preferably consisting essentially of, and even morepreferably consisting of 1-chloro-3,3,3-trifluoropropene (“1233zd”), andeven more preferably trans-1-chloro-3,3,3-trifluoropropene(“trans-HFO-1233zd or 1233zd(E)”) and a second component selected fromthe group consisting of 2,3,3,3-tetrafluoropropene (HFO-1234yf) andtrans-1,3,3,3-tetrafluoropropene (trans-HFO-1234ze). Preferred azeotropeand azeotrope-like mixtures of the invention exhibit characteristicswhich make them particularly desirable for number of applications,including as refrigerants, as blowing agents in the manufacture ofinsulating foams, and as solvents in a number of cleaning and otherapplications, as propellants, as aerosols, and as the propellant and/orthe material being sprayed in other sprayable compositions. With respectto refrigeration, the present compositions are particularly useful inmobile air conditioning, including specifically automobile airconditioning, chillers, stationary refrigeration and the like.

According to one aspect of the invention, applicants have recognizedthat these compositions tend to exhibit relatively low global warmingpotentials (“GWPs”), preferably less than about 1000, more preferablyless than about 500, more preferably less than about 150, and even morepreferably less than about 75.

One aspect of the present invention involves a composition comprising(a) a binary azeotrope-like mixture consisting essentially of1-chloro-3,3,3-trifluoropropene and a second component selected fromselected from the group consisting of 2,3,3,3-tetrafluoropropene(HFO-1234yf) and trans-1,3,3,3-tetrafluoropropene (trans-HFO-1234ze);and (b) at least one or more adjuvant selected from: co-blowing agent,co-solvent, active ingredient, material to be sprayed, and additive suchas lubricants, stabilizers, metal passivators, corrosion inhibitors, andflammability suppressants.

Another aspect of the invention provides a solvent for use in vapordegreasing, cold cleaning, wiping and similar solvent applicationscomprising an azeotrope-like mixture as described herein. According toanother aspect of the invention, the present compositions are useful inconnection with the refrigeration systems, compositions and methodswherein the composition is used as a refrigerant with enhanced oilreturn properties and/or as an oil return agent to enhance solubility ofanother refrigerant in the lubricating oil used in the refrigerationsystem/method. According to one embodiment of this aspect of theinvention, the lubricant which is used in the refrigerant systempreferably comprises, and in certain embodiments consists essentiallyof, polyalkylene glycol lubricant. The present compositions also haveadvantage in connection with refrigerant systems that include alubricant which comprises mineral oil, either alone or together withother lubricating components.

Another aspect of the invention provides a sprayable compositioncomprising an azeotrope-like mixture as described herein, an activeingredient and/or material to be sprayed or applied, and, optionally,inert ingredients and/or solvents and/or other aerosol propellants.

Yet another aspect of the invention provides closed cell foam comprisinga polyurethane-, polyisocyanurate-, or phenolic-based cell wall and acell gas disposed within at least a portion of the cell wall structure,wherein the cell gas comprises the azeotrope-like mixture as describedherein.

According to another embodiment, provided is a polyol premix comprisingthe azeotrope-like mixture described herein.

According to another embodiment, provided is a foamable compositioncomprising the azeotrope-like mixture described herein.

According to another embodiment, provided is a method for producingthermoset foam comprising (a) adding a blowing agent comprising anazeotrope-like composition according to claim 1 to a foamable mixturecomprising a thermosetting resin; (b) reacting said foamable mixture toproduce a thermoset foam; and (c) volatilizing said azeotrope-likecomposition during said reacting.

According to another embodiment, provided is a method for producingthermoplastic foam comprising (a) adding a blowing agent comprising anazeotrope-like composition according to claim 1 to a foamable mixturecomprising a thermoplastic resin; (b) reacting said foamable mixture toproduce a thermoplastic foam; and (c) volatilizing said azeotrope-likecomposition during said reacting.

According to another embodiment, provided is a thermoplastic foam havinga cell wall comprising a thermoplastic polymer and a cell gas comprisingan azeotrope-like mixture as described herein. Preferably, thethermoplastic foam comprises a cell gas having an azeotrope-like mixtureas described herein and having a cell wall constructed of athermoplastic polymer selected from polystyrene, polyethylene,polypropylene, polyvinyl chloride, polytheyeneterephthalate orcombinations thereof.

According to another embodiment, provided is a thermoset foam having acell wall comprising a thermosetting polymer and a cell gas comprisingan azeotrope-like mixture as described herein. Preferably, the thermosetfoam comprises a cell gas having an azeotrope-like mixture as describedherein and a cell wall comprising a thermoset polymer selected frompolyurethane, polyisocyanurate, phenolic, epoxy, or combinationsthereof.

According to another embodiment of the invention, provided is arefrigerant comprising an azeotrope-like mixture as described herein.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 provides an illustration of the testing apparatus used fortesting blowing agent functionality of the azeotropic compounds of thepresent invention.

DESCRIPTION OF PREFERRED EMBODIMENTS

According to certain embodiments, the present invention providesazeotrope-like compositions comprising, preferably consistingessentially of, and even more preferably consisting of1-chloro-3,3,3-trifluoropropene (“1233zd”), and even more preferablytrans-1-chloro-3,3,3-trifluoropropene (“trans-HFO-1233zd or 1233zd(E)”)and a second component selected from the group consisting of2,3,3,3-tetrafluoropropene (HFO-1234yf) andtrans-1,3,3,3-tetrafluoropropene (trans-HFO-1234ze). Thus, the presentinvention overcomes the aforementioned shortcomings by providingazeotrope-like compositions that are, in preferred embodiments,substantially free of CFCs, HCFCs, and HFCs and have very low globalwarming potentials, low ozone depletion potential, and/or no or mildflammability and which exhibit relatively constant boiling pointcharacteristics.

As used herein, the term “mildly flammable” refers to compounds orcompositions which are classified as being 2L in accordance with ASHRAEstandard 34 dated 2010, incorporated herein by reference.

As used herein, the term “azeotrope-like” relates to compositions thatare strictly azeotropic or that generally behave like azeotropicmixtures. An azeotropic mixture is a system of two or more components inwhich the liquid composition and vapor composition are equal at thestated pressure and temperature. In practice, this means that thecomponents of an azeotropic mixture are constant-boiling or essentiallyconstant-boiling and generally cannot be thermodynamically separatedduring a phase change. The vapor composition formed by boiling orevaporation of an azeotropic mixture is identical, or substantiallyidentical, to the original liquid composition. Thus, the concentrationof components in the liquid and vapor phases of azeotrope-likecompositions change only minimally, if at all, as the composition boilsor otherwise evaporates. In contrast, boiling or evaporatingnon-azeotropic mixtures changes the component concentrations in theliquid phase to a significant degree.

As used herein, the term “consisting essentially of”, with respect tothe components of an azeotrope-like composition, means the compositioncontains the indicated components in an azeotrope-like ratio, and maycontain additional components provided that the additional components donot form new azeotrope-like systems. For example, azeotrope-likemixtures consisting essentially of two compounds are those that formbinary azeotropes, which optionally may include one or more additionalcomponents, provided that the additional components do not render themixture non-azeotropic and do not form an azeotrope with either or bothof the compounds.

The term “effective amounts” as used herein refers to the amount of eachcomponent which, upon combination with the other component, results inthe formation of an azeotrope-like composition of the present invention.

Unless otherwise specified, the term 1233zd means the cis-isomer, thetrans-isomer, or some mixture thereof.

As used herein, the term cis-1233zd with respect to a component of anazeotrope-like mixture, means the amount cis-1233zd relative to allisomers of −1233zd in azeotrope-like compositions is at least about 95%,more preferably at least about 98%, even more preferably at least about99%, even more preferably at least about 99.9%. In certain preferredembodiments, the cis-1233zd component in azeotrope-like compositions ofthe present invention is essentially pure cis-1233zd.

As used herein, the term trans-1233zd with respect to a component of anazeotrope-like mixture, means the amount trans-1233zd relative to allisomers of 1233zd in azeotrope-like compositions is at least about 95%,more preferably at least about 98%, even more preferably at least about99%, even more preferably at least about 99.9%. In certain preferredembodiments, the trans-1233zd component in azeotrope-like compositionsof the present invention is essentially pure trans-1233zd.

The term HFO-1234ze is used herein generically to refer to1,1,1,3-tetrafluoropropene, independent of whether it is the cis- ortrans-form. The terms “cis-HFO-1234ze” and “trans-HFO-1234ze” are usedherein to describe the cis- and trans-forms of1,3,3,3-tetrafluoropropene respectively. The term “HFO-1234ze” thereforeincludes within its scope cis-HFO-1234ze, trans-HFO-1234ze, and allcombinations and mixtures of these.

As used herein, the term trans-HFO-1234ze with respect to a component ofan azeotrope-like mixture, means the amount trans-HFO-1234ze relative toall isomers of trans-HFO-1234ze in azeotrope-like compositions is atleast about 95%, more preferably at least about 98%, even morepreferably at least about 99%, even more preferably at least about99.9%. In certain preferred embodiments, the trans-HFO-1234ze componentin azeotrope-like compositions of the present invention is essentiallypure trans-HFO-1234ze.

As used herein, the term “ambient pressure” with respect to boilingpoint data means the atmospheric pressure surrounding the relevantmedium. In general, ambient pressure is 14.7 psia, but could vary +/−0.5psi.

The azeotrope-like compositions of the present invention can be producedby combining effective amounts of 1233zd with one or more othercomponents, preferably in fluid form. Any of a wide variety of methodsknown in the art for combining two or more components to form acomposition can be adapted for use in the present methods. For example,1233zd and trans-HFO-1234ze can be mixed, blended, or otherwise combinedby hand and/or by machine, as part of a batch or continuous reactionand/or process, or via combinations of two or more such steps. In lightof the disclosure herein, those of skill in the art will be readily ableto prepare azeotrope-like compositions according to the presentinvention without undue experimentation.

Fluoropropenes, such as CF₃CCl═CH₂, can be produced by known methodssuch as catalytic vapor phase fluorination of various saturated andunsaturated halogen-containing C3 compounds, including the methoddescribed in U.S. Pat. Nos. 2,889,379; 4,798,818 and 4,465,786, each ofwhich is incorporated herein by reference.

EP 974,571, also incorporated herein by reference, discloses thepreparation of 1,1,1,3-chlorotrifluoropropene by contacting1,1,1,3,3-pentafluoropropane (HFC-245fa) in the vapor phase with achromium based catalyst at elevated temperature, or in the liquid phasewith an alcoholic solution of KOH, NaOH, Ca(OH)2 or Mg(OH)2. The endproduct is approximately 90% by weight of the trans isomer and 10% byweight cis. Preferably, the cis isomers are substantially separated fromthe trans forms so that the resultant preferred form of1-chloro-3,3,3-trifluoropropene is more enriched in the cis isomer.Because the cis isomer has a boiling point of about 40° C. in contrastwith the trans isomer boiling point of about 20° C., the two can easilybe separated by any number of distillation methods known in the art.However, a preferred method is batch distillation. According to thismethod, a mixture of cis and trans 1-chloro-3,3,3-trifluoropropene ischarged to the reboiler. The trans isomer is removed in the overheadleaving the cis isomer in the reboiler. The distillation can also be runin a continuous distillation where the trans isomer is removed in theoverhead and the cis isomer is removed in the bottom. This distillationprocess can yield about 99.9+% puretrans-1-chloro-3,3,3-trifluoropropene and 99.9+%cis-1-chloro-3,3,3-trifluoropropene.

Trans-1233zd/Trans-HFO-1234ze Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition compriseseffective amounts of trans-1233zd and trans-HFO-1234ze. More preferably,these binary azeotrope-like compositions consist essentially of about 80to about 99.9 wt. % trans-HFO-1234ze and from about 0.1 to about 20 wt.% trans-1233zd, more preferably from about 83 to about 99.9 wt. %trans-HFO-1234ze and about 0.1 to about 17 wt. % trans-1233zd, and evenmore preferably from about 97 to about 99.7 wt. % trans-HFO-1234ze andfrom about 0.3 to about 3 wt. % trans-1233zd.

Preferably, the trans-1233zd/trans-HFO-1234ze compositions of thepresent invention have a boiling point of about −18.5±1° C. at ambientpressure as defined herein.

Trans-1233zd/HFO-1234yf Azeotrope-Like Compositions:

In a preferred embodiment, the azeotrope-like composition compriseseffective amounts of trans-1233zd and HFO-1234yf. More preferably, thesebinary azeotrope-like compositions consist essentially of about 75 toabout 99.9 wt. % HFO-1234yf and from about 0.1 to about 25 wt. %trans-1233zd, more preferably from about 85 to about 99.9 wt. %HFO-1234yf and about 0.1 to about 15 wt. % trans-1233zd, and even morepreferably from about 90 to about 99.9 wt. % HFO-1234yf and from about0.1 to about 10 wt. % trans-1233zd.

Preferably, the trans-1233zd/HFO-1234yf compositions of the presentinvention have a boiling point of about −28.5±1° C. at ambient pressureas defined herein.

The azeotrope-like compositions of the present invention may furtherinclude a variety of optional additives including, but not limited to,lubricants, stabilizers, metal passivators, corrosion inhibitors,flammability suppressants, and the like. Examples of suitablestabilizers include diene-based compounds, and/or phenol compounds,and/or epoxides selected from the group consisting of aromatic epoxides,alkyl epoxides, alkenyl epoxides, and combinations of two or morethereof. Preferably, these optional additives do not affect the basicazeotrope-like characteristic of the composition.

Heat Transfer Compositions

The compositions of the present invention are generally adaptable foruse in heat transfer applications, that is, as a heating and/or coolingmedium, including as evaporative cooling agents.

In connection with evaporative cooling applications, the compositions ofthe present invention are brought in contact, either directly orindirectly, with a body to be cooled and thereafter permitted toevaporate or boil while in such contact, with the preferred result thatthe boiling fluid in accordance with the present composition absorbsheat from the body to be cooled. In certain of such applications it maybe preferred to utilize the compositions of the present invention,preferably in liquid form, by spraying or otherwise applying the liquidto the body to be cooled. In other evaporative cooling applications, itmay be preferred to permit a liquid composition in accordance with thepresent intention to escape from a relatively high pressure containerinto a relatively lower pressure environment wherein the body to becooled is in contact, either directly or indirectly, with the containerenclosing the liquid composition of the present invention, preferablywithout recovering or recompressing the escaped gas. One particularapplication for this type of embodiment is the self cooling of abeverage, food item, novelty item or the like. Previous to the inventiondescribed herein, prior compositions, such as HFC-152a and HFC-134a wereused for such applications. However, such compositions have recentlybeen looked upon negatively in such application because of the negativeenvironmental impact caused by release of these materials into theatmosphere. For example, the United States EPA has determined that theuse of such prior chemicals in this application is unacceptable due tothe high global warming nature of these chemicals and the resultingdetrimental effect on the environment that may result from their use.The compositions of the present invention should have a distinctadvantage in this regard due to their low global warming potential andlow ozone depletion potential, as described herein. Additionally, thepresent compositions are expected to also find substantial utility inconnection with the cooling of electrical or electronic components,either during manufacture or during accelerated lifetime testing. In aaccelerated lifetime testing, the component is sequentially heated andcooled in rapid succession to simulate the use of the component. Suchuses would therefore be of particular advantage in the semiconductor andcomputer board manufacturing industry. Another advantage of the presentcompositions in this regard is they are expected to exhibit ascontagious electrical properties when used in connection with suchapplications. Another evaporative cooling application comprises methodsfor temporarily causing a discontinuation of the flow of fluid through aconduit. Preferably, such methods would include contacting the conduit,such as a water pipe through which water is flowing, with a liquidcomposition according to the present invention and allowing the liquidcomposition of the present invention to evaporate while in contact withthe conduit so as to freeze liquid contained therein and therebytemporarily stop the flow of fluid through the conduit. Such methodshave distinct advantage in connection with enabling the service or otherwork to be performed on such conduits, or systems connected to suchconduits, at a location downstream of the location at which the presentcomposition is applied.

Although it is contemplated that the compositions of the presentinvention may include the compounds of the present invention in widelyranging amounts, it is generally preferred that refrigerant compositionsof the present invention comprise the present azeotrope orazeotrope-like composition in an amount that is at least about 50% byweight, more preferably at least about 70% by weight, and even morepreferably at least about 90% by weight, of the refrigerant composition.

The relative amount of the hydrofluoroolefin used in accordance with thepresent invention is preferably selected to produce a heat transferfluid which has the required heat transfer capacity, particularlyrefrigeration capacity, and preferably is at the same time non-flammableor mildly flammable. As used herein, the term non-flammable refers to afluid which is non-flammable in all proportions in air as measured byASTM E-681.

The compositions of the present invention may include other componentsfor the purpose of enhancing or providing certain functionality to thecomposition, or in some cases to reduce the cost of the composition. Forexample, heat transfer compositions according to the present invention,especially those used in vapor compression systems, include in additionto the refrigerant comprising the present azeotrope or azeotrope-likecomposition, a lubricant, generally in amounts of from about 30 to about50 percent by weight of the composition. Furthermore, the presentcompositions may also include a co-refrigerant, or compatibilizer, suchas propane, for the purpose of aiding compatibility and/or solubility ofthe lubricant. Such compatibilizers, including propane, butanes andpentanes, are preferably present in amounts of from about 0.5 to about 5percent by weight of the composition. Combinations of surfactants andsolubilizing agents may also be added to the present compositions to aidoil solubility, as disclosed by U.S. Pat. No. 6,516,837, the disclosureof which is incorporated by reference. Commonly used refrigerationlubricants such as Polyol Esters (POEs) and Poly Alkylene Glycols(PAGs), PAG oils, silicone oil, mineral oil, alkyl benzenes (ABs) andpoly(alpha-olefin) (PAO) that are used in refrigeration machinery withhydrofluorocarbon (HFC) refrigerants may be used with the refrigerantcompositions of the present invention. Commercially available mineraloils include Witco LP 250 (registered trademark) from Witco, Zerol 300(registered trademark) from Shrieve Chemical, Sunisco 3GS from Witco,and Calumet R015 from Calumet. Commercially available alkyl benzenelubricants include Zerol 150 (registered trademark). Commerciallyavailable esters include neopentyl glycol dipelargonate, which isavailable as Emery 2917 (registered trademark) and Hatcol 2370(registered trademark). Other useful esters include phosphate esters,dibasic acid esters, and fluoroesters. In some cases, hydrocarbon basedoils are have sufficient solubility with the refrigerant that iscomprised of an iodocarbon, the combination of the iodocarbon and thehydrocarbon oil might more stable than other types of lubricant. Suchcombination may therefore be advantageous. Preferred lubricants includepolyalkylene glycols and esters. Polyalkylene glycols are highlypreferred in certain embodiments because they are currently in use inparticular applications such as mobile air-conditioning. Of course,different mixtures of different types of lubricants may be used.

The present methods, systems and compositions are thus adaptable for usein connection with a wide variety of heat transfer systems in generaland refrigeration systems in particular, such as air-conditioning(including both stationary and mobile air conditioning systems),refrigeration, heat-pump systems, and the like. In certain preferredembodiments, the compositions of the present invention are used inrefrigeration systems originally designed for use with an HFCrefrigerant, such as, for example, HFC-134a, or an HCFC refrigerant,such as, for example, HCFC-22. The preferred compositions of the presentinvention tend to exhibit many of the desirable characteristics ofHFC-134a and other HFC refrigerants, including a GWP that is as low, orlower than that of conventional HFC refrigerants and a capacity that isas high or higher than such refrigerants and a capacity that issubstantially similar to or substantially matches, and preferably is ashigh as or higher than such refrigerants. In particular, applicants haverecognized that certain preferred embodiments of the presentcompositions tend to exhibit relatively low global warming potentials(“GWPs”), preferably less than about 1000, more preferably less thanabout 500, and even more preferably less than about 150. In addition,the relatively constant boiling nature of certain of the presentcompositions, including the azeotrope-like compositions described in theco-pending patent applications incorporated herein by reference, makesthem even more desirable than certain conventional HFCs, such as R-404Aor combinations of HFC-32, HFC-125 and HFC-134a (the combinationHFC-32:HFC-125:HFC134a in approximate 23:25:52 weight ratio is referredto as R-407C), for use as refrigerants in many applications. Heattransfer compositions of the present invention are particularlypreferred as replacements for HFC-134, HFC-152a, HFC-22, R-12 and R-500.

In certain other preferred embodiments, the present compositions areused in refrigeration systems originally designed for use with aCFC-refrigerant. Preferred refrigeration compositions of the presentinvention may be used in refrigeration systems containing a lubricantused conventionally with CFC-refrigerants, such as mineral oils,polyalkylbenzene, polyalkylene glycol oils, and the like, or may be usedwith other lubricants traditionally used with HFC refrigerants. As usedherein the term “refrigeration system” refers generally to any system orapparatus, or any part or portion of such a system or apparatus, whichemploys a refrigerant to provide cooling. Such refrigeration systemsinclude, for example, air conditioners, electric refrigerators, chillers(including chillers using centrifugal compressors), transportrefrigeration systems, commercial refrigeration systems and the like.

Many existing refrigeration systems are currently adapted for use inconnection with existing refrigerants, and the compositions of thepresent invention are believed to be adaptable for use in many of suchsystems, either with or without system modification. Many applicationsthe compositions of the present invention may provide an advantage as areplacement in smaller systems currently based on certain refrigerants,for example those requiring a small refrigerating capacity and therebydictating a need for relatively small compressor displacements.Furthermore, in embodiments where it is desired to use a lower capacityrefrigerant composition of the present invention, for reasons ofefficiency for example, to replace a refrigerant of higher capacity,such embodiments of the present compositions provide a potentialadvantage. Thus, it is preferred in certain embodiments to usecompositions of the present invention, particularly compositionscomprising a substantial proportion of, and in some embodimentsconsisting essentially of the present compositions, as a replacement forexisting refrigerants, such as: HFC-134a; CFC-12; HCFC-22; HFC-152a;combinations of pentfluoroethane (HFC-125), trifluorethane (HFC-143a)and tetrafluoroethane (HFC-134a) (the combinationHFC-125:HFC-143a:HFC134a in approximate 44:52:4 weight ratio is referredto as R-404A); combinations of HFC-32, HFC-125 and HFC-134a (thecombination HFC-32:HFC-125:HFC134a in approximate 23:25:52 weight ratiois referred to as R-407C); combinations of methylene fluoride (HFC-32)and pentfluoroethane (HFC-125) (the combination HFC-32:HFC-125 inapproximate 50:50 weight ratio is referred to as R-410A); thecombination of CFC-12 and 1,1-difluorethane (HFC-152a) (the combinationCFC-12:HFC-152a in a 73.8:26.2 weight ratio is referred to R-500); andcombinations of HFC-125 and HFC-143a (the combination HFC-125:HFC143a inapproximate 50:50 weight ratio is referred to as R-507A). In certainembodiments it may also be beneficial to use the present compositions inconnection with the replacement of refrigerants formed from thecombination HFC-32:HFC-125:HFC134a in approximate 20:40:40 weight ratio,which is referred to as R-407A, or in approximate 15:15:70 weight ratio,which is referred to as R-407D. The present compositions are alsobelieved to be suitable as replacements for the above noted compositionsin other applications, such as aerosols, blowing agents and the like, asexplained elsewhere herein.

In certain applications, the refrigerants of the present inventionpotentially permit the beneficial use of larger displacementcompressors, thereby resulting in better energy efficiency than otherrefrigerants, such as HFC-134a. Therefore the refrigerant compositionsof the present invention provide the possibility of achieving acompetitive advantage on an energy basis for refrigerant replacementapplications, including automotive air conditioning systems and devices,commercial refrigeration systems and devices, chillers, residentialrefrigerator and freezers, general air conditioning systems, heat pumpsand the like.

Many existing refrigeration systems are currently adapted for use inconnection with existing refrigerants, and the compositions of thepresent invention are believed to be adaptable for use in many of suchsystems, either with or without system modification. In manyapplications the compositions of the present invention may provide anadvantage as a replacement in systems which are currently based onrefrigerants having a relatively high capacity. Furthermore, inembodiments where it is desired to use a lower capacity refrigerantcomposition of the present invention, for reasons of cost for example,to replace a refrigerant of higher capacity, such embodiments of thepresent compositions provide a potential advantage. Thus, It ispreferred in certain embodiments to use compositions of the presentinvention, particularly compositions comprising a substantial proportionof, and in some embodiments consisting essentially of, HFO-1234(preferably any one or more of cis-HFO-1234ze, trans-HFO-1234ze,HFO-1234yf, HFO-1234yc, HFO-1234zc, HFO-1234ye(E) and HFO-1234ye(Z)) asa replacement for existing refrigerants, such as HFC-134a. In certainapplications, the refrigerants of the present invention potentiallypermit the beneficial use of larger displacement compressors, therebyresulting in better energy efficiency than other refrigerants, such asHFC-134a. Therefore the refrigerant compositions of the presentinvention, particularly compositions comprising any one or more ofcis-HFO-1234ze, trans-HFO-1234ze, HFO-1234yf, HFO-1234yc, HFO-1234zc,HFO-1234ye(E) and HFO-1234ye(Z), provide the possibility of achieving acompetitive advantage on an energy basis for refrigerant replacementapplications.

It is contemplated that the compositions of the present are adaptablefor use in chillers typically used in connection with commercial airconditioning systems. In certain of such embodiments it is preferred toinclude in the present one or more of the following additional compoundsthat may be included primarily for their impact on the heat transfercharacteristics, cost and the like. The following components may thus beincluded in the compositions as co-heat transfer fluids (orco-refrigerants in the case of cooling operations):

-   Trichlorofluoromethane (CFC-11)-   Dichlorodifluoromethane (CFC-12)-   Difluoromethane (HFC-32)-   Pentafluoroethane (HFC-125)-   1,1,2,2-tetrafluoroethane (HFC-134)-   1,1,1,2-Tetrafluoroethane (HFC-134a)-   Difluoroethane (HFC-152a)-   1,1,1,2,3,3,3-Heptafluoropropane (HFC-227ea)-   1,1,1,3,3,3-hexafluoropropane (HFC-236fa)-   1,1,1,3,3-pentafluoropropane (HFC-245fa)-   1,1,1,3,3-pentafluorobutane (HFC-365mfc)-   water-   CO₂

Blowing Agents

In another embodiment of the invention, provided are blowing agentscomprising at least one azeotrope-like mixture described herein. Polymerfoams are generally of two general classes: thermoplastic foams andthermoset foams.

Thermoplastic foams are produced generally via any method known in theart, including those described in Throne, Thermoplastic Foams, 1996,Sherwood Publishers, Hinkley, Ohio, or Klempner and Sendijarevic,Polymeric Foams and Foam Technology, 2^(nd) Edition 2004, Hander GardnerPublications. Inc, Cincinnati, Ohio. For example, extruded thermoplasticfoams can be prepared by an extrusion process whereby a solution ofblowing agent in molten polymer, formed in an extruder under pressure,is forced through an orifice onto a moving belt at ambient temperatureor pressure or optionally at reduced pressure to aid in foam expansion.The blowing agent vaporizes and causes the polymer to expand. Thepolymer simultaneously expands and cools under conditions that give itenough strength to maintain dimensional stability at the timecorresponding to maximum expansion. Polymers used for the production ofextruded thermoplastic foams include, but are not limited to,polystyrene, polyethylene (HDPE, LDPE, and LLDPE), polypropylene,polyethylene terephthalate, ethylene vinyl acetate, and mixturesthereof.

According to certain preferred aspects of the present invention, thepresent compositions are used as blowing agent, or as part of a foamablecomposition, preferably wherein the foamable composition is athermoplastic, and even more preferably a polystyrene-based formulation.Applicants have surprisingly found that the compositions of the presentinvention possess, in certain embodiments, enhanced solubility in thepolymeric component a foamable compositions, and thus have thecapability of providing foams products, and particularly closed cellfoam products, with improved physical properties and characteristics,including enhanced and unexpectedly superior cell structure and/or selldistribution and/or cell size.

A number of additives are optionally added to the molten polymersolution to optimize foam processing and properties including, but notlimited to, nucleating agents (e.g., talc), flame retardants, colorants,processing aids (e.g., waxes), cross linking agents, permeabilitymodifiers, and the like. Additional processing steps such as irradiationto increase cross linking, lamination of a surface film to improve foamskin quality, trimming and planning to achieve foam dimensionrequirements, and other processes may also be included in themanufacturing process.

In general, the blowing agent may include the azeotrope-likecompositions of the present invention in widely ranging amounts. It isgenerally preferred, however, that the blowing agents comprise at leastabout 15% by weight of the blowing agent. In certain preferredembodiments, the blowing agent comprises at least about 50% by weight ofthe present compositions, and in certain embodiments the blowing agentconsists essentially of the present azeotrope-like composition. Incertain preferred embodiments, the blowing agent includes, in additionto the present azeotrope-like mixtures, one or more co-blowing agents,fillers, vapor pressure modifiers, flame suppressants, stabilizers, andlike adjuvants.

In certain preferred embodiments, the blowing agent is characterized asa physical (i.e., volatile) blowing agent comprising the azeotrope-likemixture of the present invention. In general, the amount of blowingagent present in the blended mixture is dictated by the desired foamdensities of the final foams products and by the pressure and solubilitylimits of the process. For example, the proportions of blowing agent inparts by weight can fall within the range of about 1 to about 45 parts,more preferably from about 4 to about 30 parts, of blowing agent per 100parts by weight of polymer. The blowing agent may comprise additionalcomponents mixed with the azeotrope-like composition, includingchlorofluorocarbons such as trichlorofluoromethane (CFC-11),dichlorodifluoromethane (CFC-12), hydrochlorofluorocarbons such as1,1-dichloro-1-fluoroethane (HCFC-141b), 1-chloro-1,1-difluoroethane(HCFC-142b), chlorodifluoromethane (HCFC-22), hydrofluorocarbons such as1,1,1,2-tetrafluoroethane (HFC-134a), 1,1-difluoroethane (HFC-152a),1,1,1,3,3-pentafluoropropane (HFC-245fa), and1,1,1,3,3-pentafluorobutane (HFC-365mfc), hydrocarbons such as propane,butane, isobutane, cyclopentane, carbon dioxide, chlorinatedhydrocarbons alcohols, ethers, ketones and mixtures thereof.

In certain embodiments, the blowing agent is characterized as a chemicalblowing agent. Chemical blowing agents are materials that, when exposedto temperature and pressure conditions in the extruder, decompose toliberate a gas, generally carbon dioxide, carbon monoxide, nitrogen,hydrogen, ammonia, nitrous oxide, of mixtures thereof. The amount ofchemical blowing agent present is dependent on the desired final foamdensity. The proportions in parts by weight of the total chemicalblowing agent blend can fall within the range of from less than 1 toabout 15 parts, preferably from about 1 to about 10 parts, of blowingagent per 100 parts by weight of polymer.

In certain preferred embodiments, dispersing agents, cell stabilizers,surfactants and other additives may also be incorporated into theblowing agent compositions of the present invention. Surfactants areoptional, but preferably are added to serve as cell stabilizers. Somerepresentative materials are sold under the names of DC-193, B-8404, andL-5340 which are, generally, polysiloxane polyoxyalkylene blockco-polymers such as those disclosed in U.S. Pat. Nos. 2,834,748,2,917,480, and 2,846,458, each of which are incorporated herein byreference. Other optional additives for the blowing agent mixtureinclude flame retardants or suppressants such astri(2-chloroethyl)phosphate, tri(2-chloropropyl)phosphate,tri(2,3-dibromopropyl)-phosphate, tri(1,3-dichloropropyl)phosphate,diammonium phosphate, various halogenated aromatic compounds, antimonyoxide, aluminum trihydrate, polyvinyl chloride, and the like.

With respect to thermoset foams, in general any thermoset polymer can beused, including but not limited to polyurethane, polyisocyanurate,phenolic, epoxy, and combinations thereof. In general these foams areproduced by bringing together chemically reactive components in thepresence of one or more blowing agents, including the azeotrope-likecomposition of this invention and optionally other additives, includingbut not limited to cell stabilizers, solubility enhancers, catalysts,flame retardants, auxiliary blowing agents, inert fillers, dyes, and thelike.

With respect to the preparation of polyurethane or polyisocyanuratefoams using the azeotrope like compositions described in the invention,any of the methods well known in the art can be employed, see Saundersand Frisch, Volumes I and II Polyurethanes Chemistry and Technology(1962) John Wiley and Sons, New York, N.Y. In general, polyurethane orpolyisocyanurate foams are prepared by combining an isocyanate, a polyolor mixture of polyols, a blowing agent or mixture of blowing agents, andother materials such as catalysts, surfactants, and optionally, flameretardants, colorants, or other additives.

It is convenient in many applications to provide the components forpolyurethane or polyisocyanurate foams in preblended formulations. Mosttypically, the foam formulation is preblended into two components. Theisocyanate and optionally certain surfactants and blowing agentscomprise the first component, commonly referred to as the “A” component.The polyol or polyol mixture, surfactant, catalysts, blowing agents,flame retardant, and other isocyanate reactive components comprise thesecond component, commonly referred to as the “B” component.Accordingly, polyurethane or polyisocyanurate foams are readily preparedby bringing together the A and B side components either by hand mix forsmall preparations and, preferably, machine mix techniques to formblocks, slabs, laminates, pour-in-place panels and other items, sprayapplied foams, froths, and the like. Optionally, other ingredients suchas fire retardants, colorants, auxiliary blowing agents, water, and evenother polyols can be added as a third stream to the mix head or reactionsite. Most conveniently, however, they are all incorporated into one BComponent as described above.

Any organic polyisocyanate can be employed in polyurethane orpolyisocyanurate foam synthesis inclusive of aliphatic and aromaticpolyisocyanates. Preferred as a class are the aromatic polyisocyanates.Typical aliphatic polyisocyanates are alkylene diisocyanates such astri, tetra, and hexamethylene diisocyanate, isophorene diisocyanate,4,4′-methylenebis(cyclohexyl isocyanate), and the like; typical aromaticpolyisocyanates include m-, and p-phenylene diisocyanate, polymethylenepolyphenyl isocyanate, 2,4- and 2,6-toluenediisocyanate, dianisidinediisocyanate, bitoylene isocyanate, naphthylene 1,4-diisocyanate,bis(4-isocyanatophenyl)methene, bis(2-methyl-4-isocyanatophenyl)methane,and the like.

Preferred polyisocyanates are the polymethylene polyphenyl isocyanates,particularly the mixtures containing from about 30 to about 85 percentby weight of methylenebis(phenyl isocyanate) with the remainder of themixture comprising the polymethylene polyphenyl polyisocyanates offunctionality higher than 2.

Typical polyols used in the manufacture of polyurethane foams include,but are not limited to, aromatic amino-based polyether polyols such asthose based on mixtures of 2,4- and 2,6-toluenediamine condensed withethylene oxide and/or propylene oxide. These polyols find utility inpour-in-place molded foams. Another example is aromatic alkylamino-basedpolyether polyols such as those based on ethoxylated and/or propoxylatedaminoethylated nonylphenol derivatives. These polyols generally findutility in spray applied polyurethane foams. Another example issucrose-based polyols such as those based on sucrose derivatives and/ormixtures of sucrose and glycerine derivatives condensed with ethyleneoxide and/or propylene oxide.

Examples of polyols used in polyurethane modified polyisocyanurate foamsinclude, but are not limited to, aromatic polyester polyols such asthose based on complex mixtures of phthalate-type or terephthalate-typeesters formed from polyols such as ethylene glycol, diethylene glycol,or propylene glycol. These polyols are used in rigid laminatedboardstock, can be blended with other types of polyols such as sucrosebased polyols, and used in other polyurethane foam applications such asdescribed above.

Catalysts used in the manufacture of polyurethane foams are typicallytertiary amines including, but not limited to, N-alkylmorpholines,N-alkylalkanolamines, N,N-dialkylcyclohexylamines, and alkylamines wherethe alkyl groups are methyl, ethyl, propyl, butyl, and the like andisomeric forms thereof; and hetrocyclic amines. Typical, but notlimiting examples are triethylenediamine, tetramethylethylenediamine,bis(2-dimethylaminoethyl)ether, triethylamine, tripropylamine,tributylamine, triamylamine, pyridine, quinoline, dimethylpiperazine,piperazine, N,N-dimethylcyclohexylamine, N-ethylmorpholine,2-methylpiperazine, N,N-dimethylethanolamine, tetramethylpropanediamine,methyltriethylenediamine, and the like, and mixtures thereof.

Optionally, non-amine polyurethane catalysts are used. Typical of suchcatalysts are organometallic compounds of bismuth, lead, tin, titanium,antimony, uranium, cadmium, cobalt, thorium, aluminum, mercury, zinc,nickel, cerium, molybdenum, vanadium, copper, manganese, zirconium, andthe like. Included as illustrative are bismuth nitrate, lead2-ethylhexoate, lead benzoate, ferric chloride, antimony trichloride andantimony glycolate. A preferred organo-tin class includes the stannoussalts of carboxylic acids such as stannous octoate, stannous2-ethylhexoate, stannous laurate, and the like, as well as dialkyl tinsalts of carboxylic acids such as dibutyl tin diacetate, dibutyl tindilaurate, dioctyl tin diacetate, and the like.

In the preparation of polyisocyanurate foams, trimerization catalystsare used for the purpose of converting the blends in conjunction withexcess A component to polyisocyanurate-polyurethane foams. Thetrimerization catalysts employed can be any catalyst known to oneskilled in the art, including, but not limited to, glycine salts andtertiary amine trimerization catalysts and alkali metal carboxylic acidsalts and mixtures of the various types of catalysts. Preferred specieswithin the classes are potassium acetate, potassium octoate, andN-(2-hydroxy-5-nonylphenol)methyl-N-methylglycinate.

Dispersing agents, cell stabilizers, and surfactants can be incorporatedinto the present blends. Surfactants, which are, generally, polysiloxanepolyoxyalkylene block co-polymers, such as those disclosed in U.S. Pat.Nos. 2,834,748, 2,917,480, and 2,846,458, which are incorporated hereinby reference.

Other optional additives for the blends can include flame retardantssuch as tris(2-chloroethyl)phosphate, tris(2-chloropropyl)phosphate,tris(2,3-dibromopropyl)phosphate, tris(1,3-dichloropropyl)phosphate,diammonium phosphate, various halogenated aromatic compounds, antimonyoxide, aluminum trihydrate, polyvinyl chloride, and the like. Otheroptional ingredients can include from 0 to about 3 percent water, whichchemically reacts with the isocyanate to produce carbon dioxide. Thiscarbon dioxide acts as an auxiliary blowing agent.

Also included in the mixture are blowing agents or blowing agent blendsas disclosed in this invention. Generally speaking, the amount ofblowing agent present in the blended mixture is dictated by the desiredfoam densities of the final polyurethane or polyisocyanurate foamsproduct. The proportions in parts by weight of the total blowing agentblend can fall within the range of from 1 to about 45 parts of blowingagent per 100 parts of polyol, preferably from about 4 to about 30parts.

The polyurethane foams produced can vary in density from about 0.5 poundper cubic foot to about 40 pounds per cubic foot, preferably from about1.0 to 20.0 pounds per cubic foot, and most preferably from about 1.5 to6.0 pounds per cubic foot. The density obtained is a function of howmuch of the blowing agent or blowing agent mixture disclosed in thisinvention is present in the A and/or B components, or alternativelyadded at the time the foam is prepared.

Foams and Foamable Compositions

Certain embodiments of the present invention involve a foam comprising apolyurethane-, polyisocyanurate-, or phenolic-based cell wall and a cellgas disposed within at least a portion of the cells, wherein the cellgas comprises the azeotrope-like mixture described herein. In certainembodiments, the foams are extruded thermoplastic foams. Preferred foamshave a density ranging from about 0.5 pounds per cubic foot to about 60pounds per cubic foot, preferably from about 1.0 to 20.0 pounds percubic foot, and most preferably from about 1.5 to 6.0 pounds per cubicfoot. The foam density is a function of how much of the blowing agent orblowing agent mixture (i.e., the azeotrope-like mixture and anyauxiliary blowing agent, such as carbon dioxide, chemical blowing agentor other co-blowing agent) is present in the molten polymer. These foamsare generally rigid but can be made in various grades of softness tosuit the end use requirements. The foams can have a closed cellstructure, an open cell structure or a mixture of open and closed cells,with closed cell structures being preferred. These foams are used in avariety of well known applications, including but not limited to thermalinsulation, flotation, packaging, void filling, crafts and decorative,and shock absorption.

In other embodiments, the invention provides foamable compositions. Thefoamable compositions of the present invention generally include one ormore components capable of forming foam, such as polyurethane,polyisocyanurate, and phenolic-based compositions, and a blowing agentcomprising at least one azeotrope-like mixture described herein. Incertain embodiments, the foamable composition comprises thermoplasticmaterials, particularly thermoplastic polymers and/or resins. Examplesof thermoplastic foam components include polyolefins, such aspolystyrene (PS), polyethylene (PE), polypropylene (PP) andpolyethyleneterepthalate (PET), and foams formed therefrom, preferablylow-density foams. In certain embodiments, the thermoplastic foamablecomposition is an extrudable composition.

In certain embodiments, provided is a method for producing such foams.It will be appreciated by those skilled in the art, especially in viewof the disclosure contained herein, that the order and manner in whichthe blowing agent is formed and/or added to the foamable compositiondoes not generally affect the operability of the present invention. Forexample, in the case of extrudable foams, it is possible to mix inadvance the various components of the blowing agent. In certainembodiments, the components of the foamable composition are not mixed inadvance of introduction to the extrusion equipment or are not added tothe same location in the extrusion equipment. Thus, in certainembodiments it may be desired to introduce one or more components of theblowing agent at first location in the extruder, which is upstream ofthe place of addition of one or more other components of the blowingagent, with the expectation that the components will come together inthe extruder and/or operate more effectively in this manner. In certainother embodiments, two or more components of the blowing agent arecombined in advance and introduced together into the foamablecomposition, either directly or as part of premix which is then furtheradded to other parts of the foamable composition.

Solvent/Sprayable Compositions

In a preferred embodiment, the azeotrope-like compositions of thisinvention may be used as solvents and/or as the propellant in sprayablecompositions, either alone or in combination with other knownpropellants and/or solvents. The solvent composition comprises, morepreferably consists essentially of, and, even more preferably, consistsof the azeotrope-like compositions of the invention. In certainembodiments, the sprayable composition is an aerosol.

In certain preferred embodiments, provided is a sprayable compositioncomprising a solvent as described above, an active ingredient, andoptionally, other components such as inert ingredients, solvents, andthe like.

In another aspect, the present invention provides propellantcompositions comprising or consisting essentially of a composition ofthe present invention. In certain preferred embodiments, such propellantcomposition is preferably a sprayable composition

Suitable active materials to be sprayed include, without limitation,cosmetic materials such as deodorants, perfumes, hair sprays, cleaningsolvents, lubricants, insecticides as well as medicinal materials, suchas anti-asthma medications. The term medicinal materials is used hereinin its broadest sense to include any and all materials which are, or atleast are believe to be, effective in connection with therapeutic,diagnostic, pain relief, and similar treatments, and as such wouldinclude for example drugs and biologically active substances.

In one aspect, the present compositions may be used for propellingobjects, including solid and/or liquid objects and/or gaseous objects,by applying to such objects a force generated by the presentcomposition, such as would occur through the expansion of thecompositions of the present invention. For example, such force maypreferably be provided, at least in part, by the change of phase of thecompositions of the present invention from liquid to gas, and/or by theforce released as a result of a substantial pressure reduction as thecomposition of the present invention exits from a pressurized container.In this way, the compositions of the present invention may be used toapply a burst of force, or a sustained force to an object to bepropelled. Accordingly, the present invention comprises systems,containers and devices which include compositions of the presentinvention and which are configured to propel or move an object, either aliquid object or a solid object or a gaseous object, with the desiredamount of force. Examples of such uses include containers (such aspressurized cans and similar devices) which may be used, through thepropellant force, to unblock drains, pipes or blockages in conduits,channels or nozzles. Another application includes use of the presentcomposition to propel solid objects through the environment,particularly the ambient air, such as bullets, pellets, grenades, nets,canisters, bean bags, electrodes or other individual tethered oruntethered projectiles. In other embodiments, the present compositionsmay be used to impart motion, such as a spitting motion, to gyroscopes,centrifuges, toys or other bodies to be rotated, or to impart apropelling force to solid objects, such as fireworks, confetti, pellets,munitions and other solid objects. In other applications, the forceprovided by the compositions of the present invention may be used topush or steer bodies in motion, including rockets or other projectiles.

The propellant compositions of the present invention preferably comprisea material to be sprayed and a propellant comprising, consistingessentially of, or consisting of a composition in accordance with thepresent invention. Inert ingredients, solvents, and other materials mayalso be present in the sprayable mixture. Preferably, the sprayablecomposition is an aerosol. Suitable materials to be sprayed include,without limitation, cosmetic materials such as deodorants, perfumes,hair sprays, cleaning solvents, and lubricants, as well as medicinalmaterials such as anti-asthma medications. The term medicinal materialsis used herein in its broadest sense to include any and all materialswhich are, or at least are believe to be, effective in connection withtherapeutic treatments, diagnostic methods, pain relief, and similartreatments, and as such would include for example drugs and biologicallyactive substances. The medicinal material in certain preferredembodiments are adapted to be inhaled. The medicament or othertherapeutic agent is preferably present in the composition in atherapeutic amount, with a substantial portion of the balance of thecomposition comprising a an azeotrope or azeotrope-like composition ofthe present invention.

Aerosol products for industrial, consumer or medical use typicallycontain one or more propellants along with one or more activeingredients, inert ingredients or solvents. The propellant provides theforce that expels the product in aerosolized form. While some aerosolproducts are propelled with compressed gases like carbon dioxide,nitrogen, nitrous oxide and even air, most commercial aerosols useliquefied gas propellants. The most commonly used liquefied gaspropellants are hydrocarbons such as butane, isobutane, and propane.Dimethyl ether and HFC-152a (1,1-difluoroethane) are also used, eitheralone or in blends with the hydrocarbon propellants. Unfortunately, allof these liquefied gas propellants are highly flammable and theirincorporation into aerosol formulations will often result in flammableaerosol products.

Applicants have come to appreciate the continuing need for nonflammable,liquefied gas propellants with which to formulate aerosol products. Thepresent invention provides compositions of the present invention for usein certain industrial aerosol products, including for example spraycleaners, lubricants, and the like, and in medicinal aerosols, includingfor example to deliver medications to the lungs or mucosal membranes.Examples of this includes metered dose inhalers (MDIs) for the treatmentof asthma and other chronic obstructive pulmonary diseases and fordelivery of medicaments to accessible mucous membranes or intranasally.The present invention thus includes methods for treating ailments,diseases and similar health related problems of an organism (such as ahuman or animal) comprising applying a composition of the presentinvention containing a medicament or other therapeutic component to theorganism in need of treatment. In certain preferred embodiments, thestep of applying the present composition comprises providing a MDIcontaining the composition of the present invention (for example,introducing the composition into the MDI) and then discharging thepresent composition from the MDI.

The compositions of the present invention are capable of providingnonflammable, liquefied gas propellant and aerosols that do notcontribute substantially to global warming. The present compositions canbe used to formulate a variety of industrial aerosols or other sprayablecompositions such as contact cleaners, dusters, lubricant sprays, andthe like, and consumer aerosols such as personal care products,household products and automotive products. HFO-1234ze is particularlypreferred for use as an important component of propellant compositionsfor in medicinal aerosols such as metered dose inhalers. The medicinalaerosol and/or propellant and/or sprayable compositions of the presentinvention in many applications include, in addition to azeotrope orazeotrope-like composition of the present invention, a medicament suchas a beta-agonist, a corticosteroid or other medicament, and,optionally, other ingredients, such as surfactants, solvents, otherpropellants, flavorants and other excipients. The compositions of thepresent invention, unlike many compositions previously used in theseapplications, have good environmental properties and are not consideredto be potential contributors to global warming. The present compositionstherefore provide in certain preferred embodiments substantiallynonflammable, liquefied gas propellants having very low Global Warmingpotentials.

Flavorants and Fragrances

The compositions of the present invention also provide advantage whenused as part of, and in particular as a carrier for, flavor formulationsand fragrance formulations. The suitability of the present compositionsfor this purpose is demonstrated by a test procedure in which 0.39 gramsof Jasmone were put into a heavy walled glass tube. 1.73 grams of anazeotrope composition of the present invention comprising in one casetrans-HFO-1234ze and HFO-1234yf in another case were added to the glasstube. The tube was then frozen and sealed. Upon thawing the tube, it wasfound that the mixture had one liquid phase. The solution contained 20wt. % Jasome and 80 wt. % of the azeotrope composition of the presentinventions, thus establishing favorable use a carrier for flavorformulations and fragrances. It also establishes its potential as anextractant of biologically active compounds (such as Biomass) andfragrances, including from plant matter. In certain embodiments, it maybe preferred to use the present composition for in extractionapplications with the present fluid in its supercritical state. This another applications of involving use of the present compositions in thesupercritical or near supercritical state are described hereinafter.

Inflating Agents

One potential advantage of the compositions of the present invention isthat the preferred compositions are in a gaseous state under mostambient conditions. This characteristic allows them to fill the spacewhile not adding significantly to the weight of the space being spilled.Furthermore, the compositions of the present invention are able to becompressed or liquefied for relatively easy transportation and storage.Thus, for example, the compositions of the present invention may beincluded, preferably but not necessarily in liquid form, in a closedcontainer, such as a pressurized can, which has a nozzle therein adaptedto release the composition into another environment in which it willexist, at least for a period of time, as a pressurized gas. For example,such an application may include including the present compositions in acan adapted to connect to tires such as may be used on transportationvehicles (including cars, trucks and aircraft). Other examples inaccordance with this embodiment include the use of the presentcompositions, in a similar arrangement, to inflate air bags or otherbladders (including other protective bladders) adapted to contain, atleast for a period of time, a gaseous material under pressure.Alternatively to the use of a fixed container, such as I can, thepresent compositions may be applied in accordance with this aspect ofthe invention through a hose or other system that contains the presentcomposition, either in liquid or gaseous form, and through which it canbe introduced into such a pressurized environment as is required for theparticular application.

Solvents and Cleaning Compositions

In another embodiment of the invention, the azeotrope-like compositionsdescribed herein can be used as a solvent in cleaning various soils suchas mineral oil, rosin based fluxes, silicon oils, lubricants, etc., fromvarious substrates by wiping, vapor degreasing, or other means. Incertain preferred embodiments, the cleaning composition is an aerosol.

Methods and Systems

The compositions of the present invention are useful in connection withnumerous methods and systems, including as heat transfer fluids inmethods and systems for transferring heat, such as refrigerants used inrefrigeration, air conditioning and heat pump systems. The presentcompositions are also advantageous for in use in systems and methods ofgenerating aerosols, preferably comprising or consisting of the aerosolpropellant in such systems and methods. Methods of forming foams andmethods of extinguishing and suppressing fire are also included incertain aspects of the present invention. The present invention alsoprovides in certain aspects methods of removing residue from articles inwhich the present compositions are used as solvent compositions in suchmethods and systems.

Heat Transfer Methods and Systems

The preferred heat transfer methods generally comprise providing acomposition of the present invention and causing heat to be transferredto or from the composition, either by sensible heat transfer, phasechange heat transfer, or a combination of these. For example, in certainpreferred embodiments the present methods provide refrigeration systemscomprising a refrigerant of the present invention and methods ofproducing heating or cooling by condensing and/or evaporating acomposition of the present invention. In certain preferred embodiments,the methods for cooling, including cooling of other fluid eitherdirectly or indirectly or a body directly or indirectly, comprisecondensing a refrigerant composition comprising a composition of thepresent invention and thereafter evaporating said refrigerantcomposition in the vicinity of the article to be cooled. As used herein,the term “body” is intended to refer not only to inanimate objects butalso to living tissue, including animal tissue in general and humantissue in particular. For example, certain aspects of the presentinvention involve application of the present composition to human tissuefor one or more therapeutic purposes, such as a pain killing technique,as a preparatory anesthetic, or as part of a therapy involving reducingthe temperature of the body being treated. In certain embodiments, theapplication to the body comprises providing the present compositions inliquid form under pressure, preferably in a pressurized container havinga one-way discharge valve and/or nozzle, and releasing the liquid fromthe pressurized container by spraying or otherwise applying thecomposition to the body. As the liquid evaporates from the surface beingsprayed, the surface cools.

Certain preferred methods for heating a fluid or body comprisecondensing a refrigerant composition comprising a composition of thepresent invention in the vicinity of the fluid or body to be heated andthereafter evaporating said refrigerant composition. In light of thedisclosure herein, those of skill in the art will be readily able toheat and cool articles according to the present inventions without undueexperimentation.

Applicants have found that in the systems and methods of the presentinvention many of the important refrigeration system performanceparameters are relatively close to the parameters for R-134a. Since manyexisting refrigeration systems have been designed for R-134a, or forother refrigerants with properties similar to R-134a, those skilled inthe art will appreciate the substantial advantage of a low GWP and/or alow ozone depleting refrigerant that can be used as replacement forR-134a or like refrigerants with relatively minimal modifications to thesystem. It is contemplated that in certain embodiments the presentinvention provides retrofitting methods which comprise replacing theheat transfer fluid (such as a refrigerant) in an existing system with acomposition of the present invention, without substantial modificationof the system. In certain preferred embodiments the replacement step isa drop-in replacement in the sense that no substantial redesign of thesystem is required and no major item of equipment needs to be replacedin order to accommodate the composition of the present invention as theheat transfer fluid. In certain preferred embodiments, the methodscomprise a drop-in replacement in which the capacity of the system is atleast about 70%, preferably at least about 85%, and even more preferablyat least about 90% of the system capacity prior to replacement. Incertain preferred embodiments, the methods comprise a drop-inreplacement in which the suction pressure and/or the discharge pressureof the system, and even more preferably both, is/are at least about 70%,more preferably at least about 90% and even more preferably at leastabout 95% of the suction pressure and/or the discharge pressure prior toreplacement. In certain preferred embodiments, the methods comprise adrop-in replacement in which the mass flow of the system is at leastabout 80%, and even more preferably at least 90% of the mass flow priorto replacement.

In certain embodiments the present invention provides cooling byabsorbing heat from a fluid or body, preferably by evaporating thepresent refrigerant composition in the vicinity of the body or fluid tobe cooled to produce vapor comprising the present composition.Preferably the methods include the further step of compressing therefrigerant vapor, usually with a compressor or similar equipment toproduce vapor of the present composition at a relatively elevatedpressure. Generally, the step of compressing the vapor results in theaddition of heat to the vapor, thus causing an increase in thetemperature of the relatively high pressure vapor. Preferably in suchembodiments the present methods include removing from this relativelyhigh temperature, high pressure vapor at least a portion of the heatadded by the evaporation and compression steps. The heat removal steppreferably includes condensing the high temperature, high pressure vaporwhile the vapor is in a relatively high pressure condition to produce arelatively high pressure liquid comprising a composition of the presentinvention. This relatively high pressure liquid preferably thenundergoes a nominally isoenthalpic reduction in pressure to produce arelatively low temperature, low pressure liquid. In such embodiments, itis this reduced temperature refrigerant liquid which is then vaporizedby heat transferred from the body or fluid to be cooled.

In another process embodiment of the invention, the compositions of theinvention may be used in a method for producing heating which comprisescondensing a refrigerant comprising the compositions in the vicinity ofa liquid or body to be heated. Such methods, as mentioned hereinbefore,frequently are reverse cycles to the refrigeration cycle describedabove.

Cleaning Methods

The present invention also provides methods of removing containmentsfrom a product, part, component, substrate, or any other article orportion thereof by applying to the article a composition of the presentinvention. For the purposes of convenience, the term “article” is usedherein to refer to all such products, parts, components, substrates, andthe like and is further intended to refer to any surface or portionthereof. Furthermore, the term “contaminant” is intended to refer to anyunwanted material or substance present on the article, even if suchsubstance is placed on the article intentionally. For example, in themanufacture of semiconductor devices it is common to deposit aphotoresist material onto a substrate to form a mask for the etchingoperation and to subsequently remove the photoresist material from thesubstrate. The term “contaminant” as used herein is intended to coverand encompass such a photo resist material.

Preferred methods of the present invention comprise applying the presentcomposition to the article. Although it is contemplated that numerousand varied cleaning techniques can employ the compositions of thepresent invention to good advantage, it is considered to be particularlyadvantageous to use the present compositions in connection withsupercritical cleaning techniques. Supercritical cleaning is disclosedin U.S. Pat. No. 6,589,355, which is assigned to the assignee of thepresent invention and incorporated herein by reference. Forsupercritical cleaning applications, is preferred in certain embodimentsto include in the present cleaning compositions, in addition to theazeotrope or azeotrope-like compositions, one or more additionalcomponents, such as CO2 and other additional components known for use inconnection with supercritical cleaning applications. It may also bepossible and desirable in certain embodiments to use the presentcleaning compositions in connection with particular vapor degreasing andsolvent cleaning methods.

Flammability Reduction Methods

According to certain other preferred embodiments, the present inventionprovides methods for reducing the flammability of fluids, said methodscomprising adding a compound or composition of the present invention tosaid fluid. The flammability associated with any of a wide range ofotherwise flammable fluids may be reduced according to the presentinvention. For example, the flammability associated with fluids such asethylene oxide, flammable hydrofluorocarbons and hydrocarbons,including: HFC-152a, 1,1,1-trifluoroethane (HFC-143a), difluoromethane(HFC-32), propane, hexane, octane, and the like can be reduced accordingto the present invention. For the purposes of the present invention, aflammable fluid may be any fluid exhibiting flammability ranges in airas measured via any standard conventional test method, such as ASTME-681, and the like.

Any suitable amounts of the present compounds or compositions may beadded to reduce flammability of a fluid according to the presentinvention. As will be recognized by those of skill in the art, theamount added will depend, at least in part, on the degree to which thesubject fluid is flammable and the degree to which it is desired toreduce the flammability thereof. In certain preferred embodiments, theamount of compound or composition added to the flammable fluid iseffective to render the resulting fluid substantially non-flammable.

Flame Suppression Methods

The present invention further provides methods of suppressing a flame,said methods comprising contacting a flame with a fluid comprising acompound or composition of the present invention. Any suitable methodsfor contacting the flame with the present composition may be used. Forexample, a composition of the present invention may be sprayed, poured,and the like onto the flame, or at least a portion of the flame may beimmersed in the composition. In light of the teachings herein, those ofskill in the art will be readily able to adapt a variety of conventionalapparatus and methods of flame suppression for use in the presentinvention.

Sterilization Methods

Many articles, devices and materials, particularly for use in themedical field, must be sterilized prior to use for the health and safetyreasons, such as the health and safety of patients and hospital staff.The present invention provides methods of sterilizing comprisingcontacting the articles, devices or material to be sterilized with acomposition of the present invention comprising, in addition to theazeotrope or azeotrope-like compositions, one or more costerilizingagents. While many sterilizing agents are known in the art and areconsidered to be adaptable for use in connection with the presentinvention, in certain preferred embodiments sterilizing agent comprisesethylene oxide, formaldehyde, hydrogen peroxide, chlorine dioxide, ozoneand combinations of these. In certain embodiments, ethylene oxide is thepreferred sterilizing agent. Those skilled in the art, in view of theteachings contained herein, will be able to readily determine therelative proportions of sterilizing agent and the present compound(s) tobe used in connection with the present sterilizing compositions andmethods, and all such ranges are within the broad scope hereof. As isknown to those skilled in the art, certain sterilizing agents, such asethylene oxide, are relatively flammable components, and the compound(s)in accordance with the present invention are included in the presentcompositions in amounts effective, together with other componentspresent in the composition, to reduce the flammability of thesterilizing composition to acceptable levels.

The sterilization methods of the present invention may be either high orlow-temperature sterilization of the present invention involves the useof a compound or composition of the present invention at a temperatureof from about 250° F. to about 270° F., preferably in a substantiallysealed chamber. The process can be completed usually in less than about2 hours. However, some articles, such as plastic articles and electricalcomponents, cannot withstand such high temperatures and requirelow-temperature sterilization. In low temperature sterilization methods,the article to be sterilized is exposed to a fluid comprising acomposition of the present invention at a temperature of from about roomtemperature to about 200° F., more preferably at a temperature of fromabout room temperature to about 100° F.

The low-temperature sterilization of the present invention is preferablyat least a two-step process performed in a substantially sealed,preferably air tight, chamber. In the first step (the sterilizationstep), the articles having been cleaned and wrapped in gas permeablebags are placed in the chamber. Air is then evacuated from the chamberby pulling a vacuum and perhaps by displacing the air with steam. Incertain embodiments, it is preferable to inject steam into the chamberto achieve a relative humidity that ranges preferably from about 30% toabout 70%. Such humidities may maximize the sterilizing effectiveness ofthe sterilant which is introduced into the chamber after the desiredrelative humidity is achieved. After a period of time sufficient for thesterilant to permeate the wrapping and reach the interstices of thearticle, the sterilant and steam are evacuated from the chamber.

In the preferred second step of the process (the aeration step), thearticles are aerated to remove sterilant residues. Removing suchresidues is particularly important in the case of toxic sterilants,although it is optional in those cases in which the substantiallynon-toxic compounds of the present invention are used. Typical aerationprocesses include air washes, continuous aeration, and a combination ofthe two. An air wash is a batch process and usually comprises evacuatingthe chamber for a relatively short period, for example, 12 minutes, andthen introducing air at atmospheric pressure or higher into the chamber.This cycle is repeated any number of times until the desired removal ofsterilant is achieved. Continuous aeration typically involvesintroducing air through an inlet at one side of the chamber and thendrawing it out through an outlet on the other side of the chamber byapplying a slight vacuum to the outlet. Frequently, the two approachesare combined. For example, a common approach involves performing airwashes and then an aeration cycle.

EXAMPLES

The invention is further illustrated in the following example which isintended to be illustrative, but not limiting in any manner. For therelevant examples, an ebulliometer of the general type described bySwietolslowski in his book “Ebulliometric Measurements” (Reinhold, 1945)was used.

Example 1

An ebulliometer consisting of vacuum jacketed tube with a condenser ontop which is further equipped with a Quartz Thermometer is used. About20.58 g of 1234yf was initially charged into the ebulliometer. Then1233zd(E) was added in small, measured increments. A temperaturedepression is observed at 14.4 psia when 1233zd(E) is added to 1234yf,indicating that a binary minimum boiling azeotrope is formed. Fromgreater than about 0 to about 20 weight percent 1233zd(E), the boilingpoint of the mixture stays below the boiling point of 1234yf.

TABLE 1 T(C.) Wt. % HFO-1234yf Wt. % 1233zd(E) −28.7 100.0 0.0 −28.999.7 0.3 −29.0 99.1 0.9 −29.1 97.9 2.1 −29.2 96.8 3.2 −29.2 95.1 4.9−29.1 93.4 6.6 −28.9 89.4 10.6 −28.7 85.6 14.4 −28.5 82.2 17.8 −28.278.3 21.7

Example 2

An ebulliometer consisting of vacuum jacketed tube with a condenser ontop which is further equipped with a Quartz Thermometer is used. About20.3 g of 1234ze(E) was initially charged into the ebulliometer. Then1233zd(E) was added in small, measured increments. A temperaturedepression is observed at 14.4 psia when 1233zd(E) is added to1234ze(E), indicating that a binary minimum boiling azeotrope is formed.From greater than about 0 to about 3.3 weight percent 1233zd(E), theboiling point of the mixture stays below the boiling point of 1234yf.

TABLE 2 T(° C.) Wt. % 1234ze(E) Wt. % 1233zd(E) −19.0 100.0 0.0 −19.199.7 0.3 −19.2 99.1 0.9 −19.1 97.9 2.1 −19.0 96.7 3.3 −18.8 93.4 6.6−18.5 90.3 9.7 −18.3 87.4 12.6 −18.0 82.9 17.1

Example 3

An azeotrope-like mixture containing 98% by weight HFO-1234yf and about2% by weight trans-1233zd is loaded into an aerosol can. An aerosolvalve is crimped into place and HFC-134a is added through the valve toachieve a pressure in the can of about 20 psig. The mixture is thensprayed onto surface demonstrating that the azeotropic mixture is usefulas an aerosol. The aerosol is used effectively to spray at least oneactive ingredient selected from the group consisting of deodorants,perfumes, hair sprays, cleaning solvents, lubricants, insecticides, andmedicinal materials.

Example 4

An azeotrope-like mixture containing 90% by weight HFO-1234yf and about10% by weight trans-1233zd is loaded into an aerosol can. An aerosolvalve is crimped into place and HFC-134a is added through the valve toachieve a pressure in the can of about 20 psig. The mixture is thensprayed onto surface demonstrating that the azeotropic mixture is usefulas an aerosol. The aerosol is used effectively to spray at least oneactive ingredient selected from the group consisting of deodorants,perfumes, hair sprays, cleaning solvents, lubricants, insecticides, andmedicinal materials.

Example 5

An azeotrope-like mixture containing 80% by weight HFO-1234yf and about20% by weight trans-1233zd is loaded into an aerosol can. An aerosolvalve is crimped into place and if needed HFC-134a is added through thevalve to achieve a pressure in the can of about 20 psig. The mixture isthen sprayed onto surface demonstrating that the azeotropic mixture isuseful as an aerosol. The aerosol is used effectively to spray at leastone active ingredient selected from the group consisting of deodorants,perfumes, hair sprays, cleaning solvents, lubricants, insecticides, andmedicinal materials.

Example 6

An azeotrope-like mixture containing 98% by weight trans-HFO-1234ze andabout 2% by weight trans-1233zd is loaded into an aerosol can. Anaerosol valve is crimped into place and if needed HFC-134a is addedthrough the valve to achieve a pressure in the can of about 20 psig. Themixture is then sprayed onto surface demonstrating that the azeotropicmixture is useful as an aerosol. The aerosol is used effectively tospray at least one active ingredient selected from the group consistingof deodorants, perfumes, hair sprays, cleaning solvents, lubricants,insecticides, and medicinal materials.

Example 7

An azeotrope-like mixture containing 95% by weight trans-HFO-1234ze andabout 5% by weight trans-1233zd is loaded into an aerosol can. Anaerosol valve is crimped into place and if needed HFC-134a is addedthrough the valve to achieve a pressure in the can of about 20 psig. Themixture is then sprayed onto surface demonstrating that the azeotropicmixture is useful as an aerosol. The aerosol is used effectively tospray at least one active ingredient selected from the group consistingof deodorants, perfumes, hair sprays, cleaning solvents, lubricants,insecticides, and medicinal materials.

Example 8

An azeotrope-like mixture containing 85% by weight trans-HFO-1234ze andabout 15% by weight trans-1233zd is loaded into an aerosol can. Anaerosol valve is crimped into place and if needed HFC-134a is addedthrough the valve to achieve a pressure in the can of about 20 psig. Themixture is then sprayed onto surface demonstrating that the azeotropicmixture is useful as an aerosol. The aerosol is used effectively tospray at least one active ingredient selected from the group consistingof deodorants, perfumes, hair sprays, cleaning solvents, lubricants,insecticides, and medicinal materials.

Example 9

The coefficient of performance (COP) is a universally accepted measureof refrigerant performance, especially useful in representing therelative thermodynamic efficiency of a refrigerant in a specific heatingor cooling cycle involving evaporation or condensation of therefrigerant. In refrigeration engineering, this term expresses the ratioof useful refrigeration to the energy applied by the compressor incompressing the vapor. The capacity of a refrigerant represents theamount of cooling or heating it provides and provides some measure ofthe capability of a compressor to pump quantities of heat for a givenvolumetric flow rate of refrigerant. In other words, given a specificcompressor, a refrigerant with a higher capacity will deliver morecooling or heating power. One means for estimating COP of a refrigerantat specific operating conditions is from the thermodynamic properties ofthe refrigerant using standard refrigeration cycle analysis techniques(see for example, R. C. Downing, FLUOROCARBON REFRIGERANTS HANDBOOK,Chapter 3, Prentice-Hall, 1988).

A refrigeration/air conditioning cycle system is provided where thecondenser temperature is about 150° F. and the evaporator temperature isabout −35° F. under nominally isentropic compression with a compressorinlet temperature of about 50° F. COP is determined for severalcompositions of the present invention over a range of condenser andevaporator temperatures and reported in Table 3 below, based uponHFC-134a having a COP value of 1.00, a capacity value of 1.00 and adischarge temperature of 175° F.

TABLE 3 Approximate AZEOTROPE-LIKE Approximate Approximate DISCHARGEREFRIGERANT Relative Relative TEMPERATURE COMPOSITION COP CAPACITY (°F.) trans-HFO- 0.8-1.2 0.7-1.3 160-170 1234ze/trans- 1233zd HFO1234yf/trans- 0.8-1.21 0.7-1.3 160-170 1233zd

This example shows that the azeotrope-like compositions of the presentinvention each have an energy efficiency about equal to or better thanHFC-134a and the compressor using the present refrigerant compositionswill produce discharge temperatures which are advantageous. In certainpreferred embodiments, therefore, the present invention provides methodsfor heating or cooling an article or fluid comprising using acomposition of the present invention in which the capacity of therefrigeration system is at least about 100%, more preferably at leastabout 105% of the capacity of the same system with R-134a used as therefrigerant.

Example 10

The miscibility of the azeotrope-like compositions of the presentinvention with various refrigeration lubricants is tested. Thelubricants tested are mineral oil (C3), alkyl benzene (Zerol 150), esteroil (Mobil EAL 22 cc and Solest 120), polyalkylene glycol (PAG) oil(Goodwrench Refrigeration Oil for 134a systems), and apoly(alpha-olefin) oil (CP-6005-100). For each refrigerant/oilcombination, three compositions are tested, namely 5, 20 and 50 weightpercent of lubricant, with the balance of each being the azeotrope-likecompositions of the present invention being tested

The lubricant compositions are placed in heavy-walled glass tubes. Thetubes are evacuated, the refrigerant compound in accordance with thepresent invention is added, and the tubes are then sealed. The tubes arethen put into an air bath environmental chamber, the temperature ofwhich is varied from about −50° C. to 70° C. At roughly 10° C.intervals, visual observations of the tube contents are made for theexistence of one or more liquid phases. In a case where more than oneliquid phase is observed, the mixture is reported to be immiscible. In acase where there is only one liquid phase observed, the mixture isreported to be miscible. In those cases where two liquid phases wereobserved, but with one of the liquid phases occupying only a very smallvolume, the mixture is reported to be partially miscible.

The polyalkylene glycol and ester oil lubricants are miscible in alltested proportions over the entire temperature range.

Example 11

The compatibility of the refrigerant the azeotrope-like compositions ofthe present invention with PAG lubricating oils while in contact withmetals used in refrigeration and air conditioning systems is tested at350° C., representing conditions much more severe than are found in manyrefrigeration and air conditioning applications.

Aluminum, copper and steel coupons are added to heavy walled glasstubes. Two grams of oil are added to the tubes. The tubes are thenevacuated and one gram of refrigerant is added. The tubes are put intoan oven at 350° F. for one week and visual observations are made. At theend of the exposure period, the tubes are removed.

This procedure was done for the following combinations of oil and theazeotrope-like compositions of the present invention:

-   trans-1233zd/trans-HFO-1234ze and GM Goodwrench PAG oil-   trans-1233zd/trans-HFO-1234ze and GM Goodwrench oil PAG oil-   trans-1233zd/trans-HFO-1234ze and MOPAR-56 PAG oil-   trans-1233zd/trans-HFO-1234ze and MOPAR-56 PAG oil-   trans-1233zd/trans-HFO-1234ze and MOPAR-56 PAG oil.-   trans-1233zd/trans-HFO-1234ze and GM Goodwrench PAG oil-   tran-1233zd/HFO-1234yf and GM Goodwrench oil PAG oil-   trans-1233zd/HFO-1234yf and MOPAR-56 PAG oil-   trans-1233zd/HFO-1234yf and MOPAR-56 PAG oil-   trans-1233zd/HFO-1234yf and MOPAR-56 PAG oil.

In all cases, there is minimal change in the appearance of the contentsof the tube. This indicates that the compositions of the presentinvention are stable in contact with aluminum, steel and copper found inrefrigeration and air conditioning systems, and the types of lubricatingoils that are likely to be included in such compositions or used withsuch compositions in these types of systems

Example 12

This example illustrates the performance of the azeotrope andazeotrope-like compositions of the present invention being used as aworking fluid in a refrigerant system, High Temperature Heat Pump andOrganic Rankine Cycle system. An example of the first system is onehaving an Evaporation Temperature of about of 35° F. and a CondensingTemperature of about 150° F. For the purposes of convenience, such heattransfer systems, that is, systems having an evaporator temperature offrom about 35° F. to about 50° F. and a CT of from about 80° F. to about120° F., are referred to herein as “chiller” or “chiller AC” systems.The operation of each of such systems using R-123 for the purposes ofcomparison and a refrigeration composition of the present invention isreported in Table 4 below:

TABLE 4 Chiller Temp Conditions 40° F. ET and 95° F. CT Azeotrope ofAzeotrope of trans-1233zd trans-1233zd Performance and trans- and HFO-Property Units R-123 HFO-1234ze 1234yf Approx. Capacity Rel to R-123 %100 110-130% 100-110% Approx. COP Rel to R-123 % 100  90-110% 100-110%

As can be seen from the Table above, many of the important refrigerationsystem performance parameters are relatively close to the parameters forR-123. Since many existing refrigeration systems have been designed forR-123, or for other refrigerants with properties similar to R-123, thoseskilled in the art will appreciate the substantial advantage of a lowGWP and/or a low ozone depleting refrigerant that can be used asreplacement for R-123 or like high boiling refrigerants with relativelyminimal modifications to the system. It is contemplated that in certainembodiments the present invention provides retrofitting methods whichcomprise replacing the refrigerant in an existing system with acomposition of the present invention, preferably without substantialmodification of the design.

Example 13

This example illustrates the performance of one embodiment of thepresent invention in which a refrigerant composition comprising theazeotrope or azeotrope-like composition of the present invention used asa heat transfer fluid in a refrigerant system, High Temperature HeatPump or an Organic Rankine Cycle system. An example of the first systemis one having an Evaporation Temperature of about of 35° F. and aCondensing Temperature of about 150° F. For the purposes of convenience,such heat transfer systems, that is, systems having an evaporatortemperature of from about 35° F. to about 50° F. and a CT of from about80° F. to about 120° F., are referred to herein as “chiller” or “chillerAC” systems The operation of each of such systems using R-123 and arefrigeration composition comprising an azeotrope or azeotrope-likecomposition of the present invention is reported in Table 5 below:

TABLE 5 Chiller Temp Conditions 40° F. ET and 95° F. CT Azeotrope ofAzeotrope of trans-1233zd trans-1233zd Performance and trans- and HFO-Property Units R-123 HFO-1234ze 1234yf Approx. Capacity Rel to R-123 %100 110-120%  90-100% Approx. COP Rel to R-123 % 100  90-110% 100-110%

As can be seen from the Table above, many of the important refrigerationsystem performance parameters are relatively close to the parameters forR-123. Since many existing refrigeration systems have been designed forR-123, or for other refrigerants with properties similar to R-123, thoseskilled in the art will appreciate the substantial advantage of a lowGWP and/or a low ozone depleting refrigerant that can be used asreplacement for R-123 or like high boiling refrigerants with relativelyminimal modifications to the system. It is contemplated that in certainembodiments the present invention provided retrofitting methods whichcomprise replacing the refrigerant in an existing system with acomposition of the present invention, preferably without substantialmodification of the design.

Example 14

This example illustrates the performance of one embodiment of thepresent invention in which a refrigerant composition comprising theazeotrope or azeotrope-like composition of the present invention is usedas a replacement for HFC-134a in four refrigerant systems. The firstsystem is one have an evaporator temperature (ET) of about 20° F. andcondenser temperature (CT) of about 130° F. (Example 54A). For thepurposes of convenience, such heat transfer systems, that is, systemshaving an ET of from about 0 to about 35 and a CT of from about 80° F.to about 130° F., are referred to herein as “medium temperature”systems. The second system is one have an ET of about −10° F. and a CTof about 110° F. (Example 54B). For the purposes of convenience, suchheat transfer systems, that is, systems having an evaporator temperatureof from about −20° F. to about 20° F. and a CT of from about 80° F. toabout 130° F., are referred to herein as “refrig/freezer” systems. Thethird system is one have an ET of about of 35° F. and a CT of about 150°F. (Example 154). For the purposes of convenience, such heat transfersystems, that is, systems having an evaporator temperature of from about30° F. to about 60° F. and a CT of from about 90° F. to about 200° F.,are referred to herein as “automotive AC” systems. The fourth system isone have an ET of about 40° F. and a CT of about 60° F. (Example 54D).For the purposes of convenience, such heat transfer systems, that is,systems having an evaporator temperature of from about 35° F. to about50° F. and a CT of from about 80° F. to about 120° F., are referred toherein as “chiller” or “chiller AC” systems The operation of each ofsuch systems using R-134a and a refrigeration composition comprising anazeotrope or azeotrope-like composition based on HFO-1234yf is reportedin Tables 6A-D below:

TABLE 6A Medium Temp Conditions 20° F. ET and 130° F. CT Azeotrope oftrans-1233zd Performance Property Units R-134a and HFO-1234yf Capacity*Btu/hr 2541 2500-2550 Rel to R-134a %     95-1051% COP — 2.31   2-2.5Rel to R-134a %     95-105% Discharge Press. Psig 198.7 180-200 Rel toR-134a %     90-100% Suction Press. Psig 18.4 20-25 Rel to R-134a %   110-125% Mass Flow Lb/hr 0.673 0.958 Rel to R-134a %    130-150%*Capacity per CFM of compressor displacement (Volumetric Capacity)

TABLE 6B Refrig/Freezer Temp Conditions 10° F. ET and 110° F. CTAzeotrope of trans-1233zd Performance Property Units R-134a andHFO-1234yf Capacity* Btu/hr 1234 1280-1300 Rel to R-134a %    100-110%COP — 1.77 1.5-2.0 Rel to R-134a %     90-100% Discharge Press. psig146.4 140-150 Rel to R-134a %     95-105% Suction Press. psig 1.9 5-7Rel to R-134a %    275-350% Mass Flow lb/hr 0.342  0.4-0.45 Rel toR-134a %    115-130% *Capacity per CFM of compressor displacement(Volumetric Capacity)

TABLE 6C Auto AC Temp Conditions 35° F. ET and 150° F. CT Azeotrope oftrans-1233zd Performance Property Units R-134a and HFO-1234yf Capacity*Btu/hr 2754 2600-2630 Rel to R-134a %     90-100% COP — 1.91 1.8-1.9 Relto R-134a %     90-100% Discharge Press. psig 262.9 250-250 Rel toR-134a %     90-100% Suction Press. psig 30.4 34-35 Rel to R-134a %   110-115% Mass Flow lb/hr 0.891 1.2-1.3 Rel to R-134a %    130-140%*Capacity per CFM of compressor displacement (Volumetric Capacity)

TABLE 6D Chiller Temp Conditions 40° F. ET and 95° F. CT Azeotrope oftrans-1233zd Performance Property Units R-134a and HFO-1234yf Capacity*Btu/hr 4236 4000-4100 Rel to R-134a %     90-100% COP — 6.34 6.2-6.3 Relto R-134a %     95-100% Discharge Press. psig 113.9  113-1145 Rel toR-134a %     95-100% Suction Press. psig 35.0 35-40 Rel to R-134a %   105-115% Mass Flow lb/hr 1.034 1.2-1.3 Rel to R-134a %    120-130%*Capacity per CFM of compressor displacement (Volumetric Capacity)

As can be seen from the Tables above, many of the importantrefrigeration system performance parameters are relatively close to theparameters for R-134a. Since many existing refrigeration systems havebeen designed for R-134a, or for other refrigerants with propertiessimilar to R-134a, those skilled in the art will appreciate thesubstantial advantage of a low GWP and/or a low ozone depletingrefrigerant that can be used as replacement for R-134a or likerefrigerants with relatively minimal modifications to the system. It iscontemplated that in certain embodiments the present invention providedretrofitting methods which comprise replacing the refrigerant in anexisting system with a composition of the present invention, withoutsubstantial modification of the system. In certain preferred embodimentsthe replacement step is a drop-in replacement in the sense that nosubstantial redesign of the system is required and no major item ofequipment needs to be replaced in order to accommodate the refrigerantof the present invention.

Example 15 Polyol Foam

This example illustrates the use of blowing agent in accordance with oneof the preferred embodiments of the present invention, namely the use ofan azeotrope or azeotrope-like composition based on trans-HFO-1234ze,and the production of polyol foams in accordance with the presentinvention. The components of a polyol foam formulation are prepared inaccordance with the following Table 7:

TABLE 7 PBW Polyol Component Voranol 490 50 Voranol 391 50 Water 0.5B-8462 (surfactant) 2.0 Polycat 8 0.3 Polycat 41 3.0 trans-1233zd/ 35trans-HFO-1234ze Total 140.8 Isocyanate M-20S 123.8 Index 1.10 *Voranol490 is a sucrose-based polyol and Voranol 391 is a toluene diamine basedpolyol, and each are from Dow Chemical. B-8462 is a surfactant availablefrom Degussa-Goldschmidt. Polycat catalysts are tertiary amine based andare available from Air Products. Isocyanate M-20S is a product of BayerLLC.The foam is prepared by first mixing the ingredients thereof, butwithout the addition of blowing agent. Two Fisher-Porter tubes are eachfilled with about 52.6 grams of the polyol mixture (without blowingagent) and sealed and placed in a refrigerator to cool and form a slightvacuum. Using gas burets, about 17.4 grams of the azeotrope are added toeach tube, and the tubes are then placed in an ultrasound bath in warmwater and allowed to sit for 30 minutes. The solution produced is hazy,and a vapor pressure measurement at room temperature indicates a vaporpressure of about 70 psig indicating that the blowing agent is not insolution. The tubes are then placed in a freezer at 27° F. for 2 hours.The vapor pressure was again measured and found to be about 14-psig. Theisocyanate mixture, about 87.9 grams, is placed into a metal containerand placed in a refrigerator and allowed to cool to about 50° F. Thepolyol tubes were then opened and weighed into a metal mixing container(about 100 grams of polyol blend are used). The isocyanate from thecooled metal container is then immediately poured into the polyol andmixed with an air mixer with double propellers at 3000 RPM's for 10seconds. The blend immediately begins to froth with the agitation and isthen poured into an 8×8×4 inch box and allowed to foam. Because of thefroth, a cream time can not be measured. The foam has about a 4-minutegel time and about a 5-minute tack free time. The foam is then allowedto cure for two days at room temperature.The foam is then cut to samples suitable for measuring physicalproperties and is found to have a density of about 2 pcf. K-factors aremeasured and found to be as indicated in the following Table 83:

TABLE 8 Temperature K, BTU In/Ft² h ° F. 40° F.  0.14-0.16 75° F.0.16-2.0 110° F.  0.16-2.0

Example 16 Polystyrene Foam

This example illustrates the use of blowing agent in accordance with twopreferred embodiments of the present invention, namely the use of anazeotrope based on trans-HFO-1234ze and an azeotrope based onHFO-1234yf, and the production of polystyrene foam. A testing apparatusand protocol has been established as an aid to determining whether aspecific blowing agent and polymer are capable of producing a foam andthe quality of the foam. Ground polymer (Dow Polystyrene 685D) andblowing agent consisting essentially of trans-1233zd/trans-HFO-1234zeazeotrope and blowing agent consisting essentially oftrans-1233zd/HFO-1234yf azeotrope are combined in a vessel. A sketch ofthe vessel is illustrated in FIG. 1. The vessel volume is 200 cm³ and itis made from two pipe flanges and a section of 2-inch diameter schedule40 stainless steel pipe 4 inches long. The vessel is placed in an oven,with temperature set at from about 190° F. to about 285° F., preferablyfor polystyrene at 265° F., and remains there until temperatureequilibrium is reached.

The pressure in the vessel is then released, quickly producing a foamedpolymer. The blowing agent plasticizes the polymer as it dissolves intoit. The resulting density of the two foams thus produced using thismethod are given in Table 9 as the density of the foams produced usingtrans-HFO-1234ze and HFO-1234yf. The data show that foam polystyrene isobtainable in accordance with the present invention. The die temperaturefor R1234ze with polystyrene is about 250° F.

TABLE 9 Dow polystyrene 685D Foam density (lb/ft³) Azeotrope oftrans-1233zd Azeotrope of trans-1233zd T ° F. and trans-HFO-1234ze andHFO-1234yf 275 50-60 260 20-25 13-18 250 75-80 22-26 240 15-20This example demonstrates the performance of each composition of thepresent invention alone as a blowing agent for polystyrene foam formedin a twin screw type extruder. The apparatus employed in this example isa Leistritz twin screw extruder having the following characteristics:30 mm co-rotating screwsL:D Ratio=40:1The extruder is divided into 10 sections, each representing a L:D of4:1. The polystyrene resin was introduced into the first section, theblowing agent was introduced into the sixth section, with the extrudateexiting the tenth section. The extruder operated primarily as amelt/mixing extruder. A subsequent cooling extruder is connected intandem, for which the design characteristics were:Leistritz twin screw extruder40 mm co-rotating screwsL:D Ratio=40:1Die: 5.0 mm circularPolystyrene resin, namely Nova Chemical—general extrusion gradepolystyrene, identified as Nova 1600, is feed to the extruder under theconditions indicated above. The resin has a recommended melt temperatureof 375° F.-525° F. The pressure of the extruder at the die is about 1320pounds per square inch (psi), and the temperature at the die is about115° C.A blowing agent consisting essentially of each of the above-notesazeotropic compositions is added to the extruder at the locationindicated above, with about 0.5% by weight of talc being included, onthe basis of the total blowing agent, as a nucleating agent. Foam isproduced using the blowing agent at concentrations of 10% by weight, 12%by weight, and 14% by weight, in accordance with the present invention.The density of the foam produced is in the range of about 0.1 grams percubic centimeter to 0.05 grams per cubic centimeter, with a cell size ofabout 45 to about 70 microns. The foams, of approximately 30 millimetersdiameter, are visually of very good quality, very fine cell size, withno visible or apparent blow holes or voids.

Example 16a Polystyrene Foam

This procedure of Example 15 is repeated except that the foaming agentcomprises about 50% by weight of each of the above-notes azeotropes and50% by weight of HFC-245fa and nucleating agent in the concentrationindicated in Example 15. Foamed polystyrene is prepared at blowing agentconcentrations of approximately 10% and 12%. The density of the foamproduced is about 0.1 grams per cubic centimeter, with a cell size ofabout 200 microns. The foams, of approximately 30 millimeters diameter,are visually of very good quality, fine cell structure, with no visibleor apparent voids.

Example 16b Polystyrene Foam

This procedure of Example 15 is repeated except that the foaming agentcomprises about 80% by weight of each of the above-notes azeotropes and20% by weight of HFC-245fa and nucleating agent in the concentrationindicated in Example 15. Foamed polystyrene is prepared at blowing agentconcentrations of approximately 10% and 12%. The density of the foamproduced is about 0.1 grams per cubic centimeter, with a cell size ofabout 120 microns. The foams, of approximately 30 millimeters diameter,are visually of very good quality, fine cell structure, with no visibleor apparent voids.

Example 17 Polyurethane Foam Compressive Strength

This example demonstrates the performance of a trans-HFO-1234ze basedazeotrope of the present invention, used in combination with hydrocarbonco-blowing agents, and in particular cyclopentane co-blowing agents incompressive strength performance of polyurethane foams.

A commercially available, refrigeration appliance-type polyurethane foamformulation (foam forming agent) is provided. The polyol blend consistedof commercial polyol(s), catalyst(s), and surfactant(s). Thisformulation is adapted for use in connection with a gaseous blowingagent. Standard commercial polyurethane processing equipment is used forthe foam forming process. A gaseous blowing agent combination was formedcomprising trans-HFO-1234ze based azeotrope in a concentration ofapproximately 60 mole percent, and cyclopentane in a concentration ofapproximately 40 mole percent of the total blowing agent. This exampleillustrates the physical property performance. Table 10 below reportsthe compressive strength of similar machine-made polyurethane foamsusing a blowing agent of the present invention in comparison to foamsmade using a blowing agent consisting of HFC-245fa and a blowing agentconsisting of cyclopentane.

TABLE 10 Compressive Strength Parallel Perpendicular % Yield % YieldBlowing Agent trans-1233zd/ 13-14 14-15 HFO1234ze/cyclopentane HFC-245fa13-14 14.5-15.5 Cyclopentane 11.462 10.559

Example 18 Trans-1233zd Azeotropes as Solvent

An azeotrope based on trans-HFO-1234ze and an azeotrope based onHFO-1234yf was transferred to a glass container. A silicon lubricant,particularly a high-viscosity (12,500 cP) silicone oil, was added toeach azeotrope to a concentration of about 10 weight percent. Thisresulted in a homogeneous, single-phase solution, demonstrating thateach azeotrope dissolves silicone based lubricant oils.

Example 19 Trans-1233zd Azeotropes as Cleaning Agent

A metal coupon was coated with rosin-based solder flux and allowed todry. The coupon was weighed and then dipped in an azeotrope based ontrans-HFO-1234ze and an azeotrope based on HFO-1234yf. The coupon wasremoved, allowed to dry and reweighed to determine how much solder fluxwas removed. In duplicate runs, an average of 25% by weight of the fluxwas removed.

Example 20 Trans-1233zd Azeotropes as Extractant

A medicament, particularly a plant-derived Artemisinin which is ananti-malarial drug, is extracted from the Artemisia annua plant. Asample of Artemisinin was weighed into a vial. An azeotrope based ontrans-HFO-1234ze and an azeotrope based on HFO-1234yf was added to thevial until the Artemisinin dissolved. The results showed thatmedicaments, particularly plant-derived medicaments such as Artemisininis soluble up to approximately 3 weight percent in each azeotrope,demonstrating that it can be used to extract the drug from biomass.

Having thus described a few particular embodiments of the invention,various alterations, modifications, and improvements will readily occurto those skilled in the art. Such alterations, modifications, andimprovements, as are made obvious by this disclosure, are intended to bepart of this description though not expressly stated herein, and areintended to be within the spirit and scope of the invention.Accordingly, the foregoing description is by way of example only, andnot limiting. The invention is limited only as defined in the followingclaims and equivalents thereto.

The invention claimed is:
 1. A binary azeotrope or azeotrope-likemixture consisting essentially of from 2.1 to 6.6 weight percenttrans-1-chloro-3,3,3-trifluoropropene (trans-HFO-1233zd) and from 93.4to 97.9 weight percent 2,3,3,3-tetrafluoropropene (HFO-1234yf).
 2. Thecomposition of claim 1 further comprising at least one additionalcomponent selected from lubricants, stabilizers, metal passivators,corrosion inhibitors, flammability suppressants, and combinations ofthese.
 3. A heat transfer composition comprising a refrigerantconsisting essentially of the composition of claim
 1. 4. The heattransfer composition of claim 3 having a global warming potential (GWP)of less than about
 1000. 5. The heat transfer composition of claim 3having a global warming potential (GWP) of less than about
 500. 6. Theheat transfer composition of claim 3 having a global warming potential(GWP) of less than about
 150. 7. The heat transfer composition of claim3 having a global warming potential (GWP) of less than about
 75. 8. Theheat transfer composition of claim 3 classified as being 2L according toASHRAE standard 34 dated
 2010. 9. A heat transfer method comprisingtransferring heat by causing a phase change in the composition ofclaim
 1. 10. The composition of claim 1 further comprising at least oneadditional component selected from co-blowing agent, co-solvent, activeingredient, a material to be sprayed, lubricants, stabilizers, metalpassivators, corrosion inhibitors, flammability suppressants, solventsand combinations of these.
 11. A solvent composition comprising thecomposition of claim
 1. 12. A cleaning method comprising applying thesolvent composition of claim 11 to a material or object to be cleaned.13. The cleaning method of claim 12 wherein said applying step comprisesspraying.
 14. The cleaning method of claim 12 comprising vapordegreasing.
 15. A sprayable composition comprising the composition ofclaim
 1. 16. The sprayable composition of claim 15 in the form of anaerosol.
 17. A blowing agent comprising the composition of claim
 1. 18.A closed cell foam comprising a polyurethane-, polyisocyanurate-, orphenolic-based cell wall and a cell gas disposed within at least aportion of the cell wall structure, wherein the cell gas comprises theblowing agent of claim
 17. 19. A polyol premix composition comprisingthe blowing agent of claim
 17. 20. A foamable composition comprising theblowing agent of claim
 17. 21. The composition of claim 1 wherein saidbinary azeotrope or azeotrope-like mixture is an azeotropic composition.